Reaction product of epoxidized monohydric alcohol esters and hydroxylated tertiary monoamines



amine, on the other hand.

The products herein described may be employed for l 2,828,323 REACTION PRODUCT 0F EPOXIDIZED wave- 7 HYDRIC ALCOHOL ESTERS AND HYDROXYL- ATED TERTIARY MONOAMINES V.

Melvin De Groote and Jen-Pu Cheng, University 'ity, Mo., assignors to Petrolite Corporation, Wilmington, Del.,acorporation,of Delaware l t No Drawing. Application April 13, 1956 Serial No. 577,957

Claims. (or. 260-404) The present invention is concerned with the reaction products of certain epoxidized monohydric alcohol esters of fatty acids and particularly the low molal alcohol esters of naturally-occurring fatty acids and modified naturallyoccurring fattyacids on.the one hand and a hydroxylated tertiary monoamine, and preferably a basic tertiary mono,-

a large variety of purposes, either as such or after con- 7 version into salts.

The products also may be used as intermediates for further reaction. For purpose of convenience what is will be divided into six parts:

Part 1 is concerned with the derivatives obtained by the epoxidation of fatty acid esters of mon ohydric alcohols and generally characterized by the presence of at least one oxiranering per fatty acid molecule; Part 2 is concerned with hydroxylated tertiary mon said hereinafter amines and particularly basic tertiary monoamines which pared by further reaction with the products described in Part 3 by the use of some additional reactant, such as an alkylene oxide or the like. Furthermore, in many instances the products obtained in the manner described in Part 3, preceding, can be heated without the addition of any other reactant so that ring formation or other reactions take place, thus yielding a completely different series of products.

The formula for 9,10-epoxystearic acid is as follows:

If instead of a fatty acid one employed an ester, particularly an ester of a monohydricalcohol, the corresponding formula would be as follows:

In actual practice commercially available epoxidized esters of a monohydric alcohol represent a product which may vary from a 70% or 75% yield up to 80% or even 85% or 90%, based onthe presence of a single oxirane ring per fatty acid radical as representing 100% yield.

In our co-pending application, Serial No. 532,121, filed September 1, 1955, we have described a broad genus of compounds obtained by. the process of reacting (A) an United States atent V 7 2,828,313 Patented Mar. 25, 1358 a 2 oxirane ring-containing compound obtained by epoxidation of an epoxidation-susceptible fatty acid, fatty acid ester, fatty acid amide or fatty alcohol with (B) an oxyalkylation-susceptible compoundhaving at least one labile hydrogen atom.

The present invention is concerned with a sub-genus or specie related to the aforementioned generic invention described in our co-p ending application, Serial No. 532,121, filed September 1, 19,55. The present invention is limited to reactions involving epoxidized monohydric alcohol esters having at least one and not over 2 oxirane rings per fatty acidhmolecule and hydroxylated tertiary monoamines such as triethanolamine,.ethyl .diethanolamine. etc.

Such epoxidizedester and preferably one showing approximately one Joxirane ring per acyl radicalis reacted 'with a mole of a hydroxylated monoamine as described. Theoretically at least one mole of a hydroxylated monoamine can be caused to react with at least the same number of oxirane rings as appears in the ester, i. e., from one to 2 moles of the amine for each mole ofthe monohydric alcoh'o l'elstera Bearing in mind the ester can also react to form a simpleamidein the same way that the unepoxidized ester can so react it is obvious that eachmole of epoxidized ester can be reacted with at least 2 moles of a hydroxylated monoamine is give an amine ester. Also, it is obvious one can react one 'mole of such amine with 2 or more'moles of the epoxidized'monohydric alcohol ester.

Although the reactions'herein involved invariably and inevitably include a reaction involving a monoamine and an oxirane ring, the complexity of reaction goes further than has been previously indicated. One aspect is the fact'that the oxirane ring may be ruptured to produce isomers.

Also, if for convenience one indicated the epoXidized acid as R-A--RCOOH and the monohydric alcohol derivative as RAR'COOR it is obvious that one amine,

as previously indicated, may unite 2 such esters as indicated bythe following, provided a monoamine has at least 2 hydroxyl groups as in the case of ethyldithanolamine:

with at least 2 other molecules having at least a single reactive'hydrogen atom. a

Since the ester, like any other fatty acid equivalent, could act as an acylating agent it is obvious that hydroxyamine esters could be formed. For that matter a product of the kind previously described could be reacted with a large number of polyamino compounds, such as ethylenediamine, triethylenetetramine, tetraethylene pentamine, etc., with particular reference'to the polyamines described not only in our aforementioned co-pending application, Serial No. 532,121, but also in our two subsequently filed applications,.Se1-ial Nos. 548,748, and 548,749, both filed November 23, 1955.

However, having obtained a reaction product in the manner described above by using ethyldiethanolamine, methyl diethanolamine, triethanolamine, or the like with or without o xyalkylation particularly using. ethylene asaaaae oxide, propylene oxide, or butylene oxide, one can obtain an ester in a manner similar to the formation of an amide by reaction with a polyamine. One can show the amide formation thus:

R-AR C N z s "C iH'iNH:

amine radical As a matter of'fact, the compounds obtained in the above manner, i. e., using a polyamine which can or cannot be subjected to further reaction such as the formation of the cyclic amidine ring represents an important sub-genus of the present invention. a i It is well known, of course, thaftlieTamides of-polyamines which are characterized by a primary amino radical and a secondary amino ra'dical separated by 2 or 3 carbon atoms on heating yield cyclic amidines and in the case of polyethylene amines yield imidazolines. Various derivatives, of course, also are obtainablesuch as amido imidazolines, etc. Without going further into the complexity of the invention as herein stated it is obvious it includes a variety of materials resulting from an initial reaction of an oxirane ring as specified and .may result in amidification with the formation of cyclic arnidines at a point above the initial reaction temperature and a point below pyrolysis. The formation of amides or cyclic amidinesmay be varied by the addition of more monocarboxy acids; in fact, ditferent carboxy acids may be added. Or if desired one can add dicarboxy acids. For this reason the present invention is limited merely to the reaction involving the rupture of the oxirane ring, subject to certain qualifications. I p 7 Although esters of various monohydric alcohols'can be employed for any one of a number of reasons, our preference is to use low molal aliphatic alcohols and particularly butyl alcohol, i. e., the butyl ester. If such ester is derived from a polyethylenic acid in which a number of oxirane rings can be introduced one could, of course, have as many as 2 oxirane rings per acyl radical. This would also be the case if butyl ricinoleate, for example, were esterified with oleic acid or soybean fatty acid. Here, again, an oxirane ring could be introduced in the ricinoleyl radical and also in the unsaturated radical which had been linked by virtue of the ricinoleyl hydroxyl radical. Similarly, soybean fatty acid can be esterified with high molal unsaturated alcohols such as those derived from soybean oil and :the like. In such instances an oxirane ring could be introduced in both the acyl radical position and the falcohol'residue position. Going a step further, one might esjterify ricinoleic acid with oleyl alcohol and then acylate with oleic acid and thus produce an ester of a monohydric alcohol in which 3 oxirane rings'could be introduced. However, as previously noted, for various reasons and particularly for economy and simplicity of reaction our preference-is to use esters such as the butyl ester of soybean fatty acid, the amyl ester of soybean fatty acid, etc.

PART 1 The epoxidation of ethylenic compounds and particularly esters of unsaturated fatty acids, unsaturated aliphatic alcohols, and the unsaturated fatty acids themselves, is well known. For instance, it has been described in the following patents: I I

U. S. Patent Nos. 2,443,280; 2,445,892; 2,457,328; 70 2,458,484; 2,485,160; 2,487,829; 2,510,905; 2,556,145; 2,567,237; 2,567,930;'2,569,502;' 2,661,367; 2,686,805;

2,692,271. a a e I Additionally epoxidation "procedures havef been de- 'scrib'ediathe trade"li'terature'of organizations-"vvhicli 75 supply one or more reactants employed in the procedure. For instance, see Bulletin P63-355 entitled Hydrogen Peroxide-Resin Technique for the Preparation of Peracetic Acid, E. I. du Pont de Nemours & Company; Bulletin P6l-454 entitled Hydrogen Peroxide-Resin Technique for Epoxidation of Unsaturated Fats, Oils, and Derivatives, E. I. du Pont de Nemours & Company; and booklet entitled Hydrogen Peroxide, issued by Buffalo Electro-Chemical Company, Inc. See also Chemical Week, August 21, 1945, page and Chemica-l Week, December 25, 1954, page 32.

An excellent brief description is found in aforementioned U. S. Patent No. 2,692,271, dated October 19, 1954, to Greenspan et a1. What is said immediately following is substantially as it appears in said patent.

In broad aspect, epoxidation comprises a reaction at a point of unsaturation of the ethylene type in a carbon compound whereby the unsaturated linkage is by the addition of oxygen changed to an oxirane compound.

Many methods of epoxidation have been suggested. For instance, the ethylene linkage has been reacted upon by the employment of perbenzoic acid in a non-aqueous solvent such-as chloroform and peracetic acid used in aqueous solution. Many other peracids have been found effective as epoxidizing agents, perphthalic and percamphoric', among others.

In general, epoxidation of the olefinic compound has been found to proceed best by the employment of peracetic acid and other similar per-compounds. Swern, in U. S. Patent 2,411,762, recommends that epoxidation be performed in special organic solvents, while Terry and Wheeler in 2,458,484 perform epoxidation under vigorous agitation of an aqueous solution of peracetic acid and an insoluble long chain olefinic material. See also Findley et a1. JJA. C. S. 67, 412-414 (1945). All of these investigators recognize the necessity of maintaining relatively low temperatures'in order to favor the'formation of the epoxy compound and to lessen'the production,

tions are available for. use.

When the olefinic linkage is reacted with a peracid, it is possible to obtain either or both of two end products; the one being the oxirane compound which. may be illustrated broadly as u that is the epoxy compoundflhe other being the glycol,

formation, although in general the oxirane ring may be considered to be opened up with the production of a glycol by reaction with water, or the production of the subjected to epoxidation by conventional proceduresare illustrated by the following: T V l H H R-C=CRi--COH or the carboxyl carbon atom, or what was initially the carboxyl carbon atom. For example, in the second formula, i. e., the formula of the alcohol, it will be noted of course that the carboxyl group has been converted into the terminal alcoholic radical.

In the last two formulas R" represents the ester radical which may be monohydric, dihydric, trihydr'ic, tetra hydric, etc. v

In the last formula n is a small whole number varying 'from 2 to 6 for example, which corresponds to the val- .ency of the multivalent radical R". 1

One can purchase a largevnumber of suitable-epoxidaition products in the open. market or can prepare the .same if desired. In a general way, of course, the most economical products are those derived from naturallyoccurring glycerides as, for example, soyabean oil. Usually an effort is made to obtain the lowest iodine value consistent with commercial standards. If one started with soap makers grade olive oil theoretically one might obtain a product having substantially no iodine number and 3 oxirane rings per glyceride radical. Actually, this is not the case for the reason it is difficult by most procedures to obtain an iodine value from a monoethylenic acid glyceride which is less than 10 to 20, and unusual care is required to obtain an iodine value below 10. An iodine value of 10 under such circumstances would appear to be the ultimate goal as far as present commercial procedure is concerned.

If one employs soyabean oil which contains an approximate 50% linoleic acid as a glyceride and about 35% oleic acid, one mayreadily obtain a product which has on the average 1.5 oxirane rings per fatty acid radical. If one starts with a more highly unsaturated oil, such as linseed oil, one can approximate 2 oxirane rings per fatty acid molecule.

All that has been said previously is a matter of common knowledge and is stated in brief form in aforementioned U. S. Patent No. 2,556,145, dated June 5, 1951, to Niederhauser. For instance, this patent states in substantially verbatim form as follows: i

The vegetable oils which when epoxidized may be used in practicing the present invention'are those glycerides of saturated and unsaturated acids which have a degree of unsaturation represented by an iodine value of from 90 to 205 and in which the fatty acids neitherfare hydroxylated nor possess conjugated unsaturation. The semi-drying vegetable oils, which are primarily glycerides of oleic and linoleic acids, are preferred. Among those oils which may be used are epoxidized peanut, rapeseed, cottonseed, corn, tobacco seed, cucurbit, sunflower, safflower, poppyseed, linseed, perilla, and soybean oils. Of these epoxidized oils, soybean oil is particularly efiicient. The effectiveness of the epoxidized oils in stabilizing chlorinated rubber is dependent upon both the concentration 6 infwhichithey amused and the degree to'whichthey havetbeen epoxidized; i. e., the number of epoxy groups that have been introduced. Theoretically, each carbon to carbon double bond of the original vegetable oil can be converted to an epoxy group. ln practical operation this will seldom, if ever, be attained but it is desirable that highly epoxidized oils be used so that maximum stability be effected; It is recommended that there be used epoxidized oils containing an average of from 2.5 to 6 epoxy groups per molecule. a

If the fatty acid group has some other functional group present,,dilficu'lty may be involved in obtaining optimum yields, for some reason that is not entirely clear. This would apply, for example, to castor oil, and ricinoleic acid esters. On the other hand, if castor oil is reacted with a low molal acid such as acetic acid, propionic acid,

.or thelike, then theseiditficulties appear to be eliminated.

There also appears to be difiiculty in obtaining suitable yields in the case of conjugated unsaturation. In some instances where the unsaturation is not conjugated there is. indication that there may be a shift during reaction to produce conjugation. In other words, in the epoxidation of the fatty acid or fatty acid ester or the like, if the fatty acid is polyethylenic it is very important that the ethylenic radicals be non-conjugated. The fatty acids themselvesmay contain 8 to 22 carbon atoms. The best example of the rnonoethylenic acid is, of course, oleic acid and perhaps erucic acid. Both are readily available as glycerides. As to the polyethylenic acids, particular attention-is directed to linoleic. As to an example of an acid having 3 ethylenic linkages attention is directed to linolenic; These acids, of course, are available in the form of glycerides, particularly mixed glycerides. Other polyethenoic acids are obtained from oils of aquatic origin.

The alcohols derived from the fatty acids are susceptible to epoxidation but present added difficulties by resulting in somewhat lower yields, perhaps due to the presence of the hydroxyl group. However, alcohols which are suitable for epoxidation include, among others, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, mixed arachidonylclupanodonyl, erucyl alcohol, and ricinoleyl alcohol.

When monohydric alcohol esters of polyethylenic acids are subjected to epoxidation the oxirane ring may be formed and may be opened so as to form a hydroxyl group, or a dihydroxyl group with one ring being left intact. For instance, if one-refers to the formulas that have been shown previously it becomes obvious that a radical indicated as RA- may become ()H OH R'-o b-A- If one starts with a monohydric 'alcohol ester of a hydroxylated unsaturated acid, for instance, the ethyl, methyl, or butyl ester of ricino-leic acid, it is possible to introduce a group like an acetyl group or an oleyl group and have a radical comparable to the following:

1 BI'C? RCA Reference is made to a formula which indicates the combination of the ester with a tertiary hydroxylated monoamine in a mole-for-mole ratio, thus:

in which R is the divalent radical of a hydroxylated monoamine as, for example, the reaction product of one mole of triethanolarnine and one mole of glycide.

Although the effort, as far as this invention goes, is simply to react an epoxidized monohydric alcohol ester of the kind described with an amine or other reactant of the kind described, "so as --to *open'=t he o'xirane-ring and not-*necessarilyigo any further, yetitfollows 'thm 'as onetries-to get a-high yield insuch reaction invariably and inevitablysome-other reaction, i.'-e., some sort of side reaction; may take "place. Thus, -'although the products are described as reaction products-involving an oxirane "ring' of the monohydricalcohol ester yet these side reactions may --introduce-and yieldan-appreciable amount in some instances of some of the products-herein mentioned, as for example' thecstersi 1 Again, it; has been pointed out that theoa'cyl' radical carrying the-oxirane-ring' also may contain a single-hydroxyl ortwo hydroxyls as the resultof-the' opening-of an oxirane ring by --reaction with water.- Furthermore, when the amine -reaetsiwith the oxirane ring there isa 'hydrox'ylformed on the adjacent carbon atom. Thus, 'variousreactions *may take place involving one or more of thesehydroxyl groups as, for instance,'- dehydration with the formation-of an unsaturated bond, este'rification or perhaps-even insome-instances the reformingtof .an oxirane ring from two adjacent hydroxyl groups .with possible further'reaction. All ofwhich emphasizes the complexity of the reactioninvolved, or ratherthe complexity of possibleside'reactionswhen one is attempting toproduce mainly 'andsubstantially the initial resultant "of the'amine herein described and the epoxidized reactant. The samewould apply in-reactions involving otherreactants.

It-is obvious if an unsaturated alcohol were .esterified with soyabean acidor the'like, onecould obtain a'monohydric alcohol ester which in realitywould be a wax and could be epoxidizedto introduce. 1,- 2, 3 and even 4 oxirane rings provided'that both. the alcohol radical and the fatty acid radical had at least 2 oxirane rings.

A somewhat similar situation is involved, of course, if one esteritied methyl ricinoleate or the like with unsaturated acid such as soyabean fatty acid. Under such circumstances one could readilyintroduce at least 2 and possibly 3 oxirane rings per ricinoleic acid ester.

The products obtained in the manner described herein, whether single resultants of reaction or a cogeneric mixture, are essentially products in which there has been no decomposition or degradation, and which are solvent soluble, either as such or in .thelform of salts, particularly salts of-a monocarboxy acidsuch as acetic acid, propionic acid, lactic acid, diglycolic acid, gluconic acid, etc. Solubility means solubilityin either water or a hy- -drocarbon solvent, or an oxygenatedorganic solvent, or -a mixture of the same. The intention is to differentiate from insoluble resins, orresin like materials which, could be obtained perhaps from the same reactants.

In the use of epoxidized fatty acids or their equivalents as herein described, we have limited the scope of the invention to reactions involving the formation of a hydrolysis resistant linkage, i. e., a non-ester linkage. One such reason for such limitation is thatone can readily conduct epoxidation and hydrolysisor at least cause ring opening so as to produce a dihydroxy fatty acids Such dihydroxylated compound can easily be esterified. Obviously a reaction involving .an .epoxidized fatty acid and another acid may be indicated by the following:

H H vlem e-Rumor! 0:0 R4 Inpreparing the esters of monohydric alcohols it is to be ,noted one'can use alcohols having. fairly high molecular weights, i. e., thealcohols from .fatty acids -having 16, 18-, 2 or even 22 carbon atoms. The oleyl alcohol esters oflinoleic. acid have.been-,pre ared and, similarly, the linoleyl esters. Furthermore, onecan purchasemixed bleyl linoleyl alcohols. These have vbeen esterified with various acidsnb oth monocarboxy anddi carboxy, such as dimerized linolenic acid. Such unsaturated esters have been-subjectedto-epoxidation so as to yield products having at least one. oxirane ring per ester unit and in someinstances ttwo oxirane rings per ester unit. The yield based on theory is comparatively low but still is sufficient to supply at least one oxirane ring in various compounds. of the kind herein described.

PART 2 As previously noted,-the present part is concerned with suitable hydroxylated tertiary amines which may be employed for preparing theiherein described compounds. Snchtertiary nonoamines must have at least one hydroxyl radical .and may-have two, or three or even more. For instance, if the primary amine, such as ethylamine, propylamine, butylamine, orthe'like, is reacted with 2 moles of .glycide to .formv a tertiary amine one obtains a compound having 4 hydroxyl radicals. Similarly, if a mole of triethanolarnine, tripropanolamine or tributanolamine is reacted with 3 moles of glycide one obtains the mono- -amine having as many as 6 hydroxyl radicals.

One needtnot prepare suitable amines but can purchase any one of a number of suitable tertiary monoamines which can beemployed as reactants for combination with the epoxidized derivatives. The most common examples are tri'ethanolamine, tripropanolamine and tributanolamine. Other examples include diethylethanolamine, dimethylethanolamine, dimethylisopropanolamine, dimethylbutanolamine, Nrmethyldiethanolamine, N-hyoxides as noted to yield tertiary amines. Ethylene oxide,

propylene oxide, butyleneoxide, glycide and other comparable oxides may be used. In this instance again the amounts of the oxide used can be substantial. For instance, 2 to 15 moles instead of merely enough to convert the amine into a tertiaryamine.

"Other suitable monoamines which may be employed as 'such, or after-treatment with 1, 2 or morermoles of alkylene oxide ofthe kind described, include the following: n-Butyl amine Dibutyl amine 2ethylhexylamine Di Z-ethylhexyl) amine Diethylethanolamine N-butyl diethanolamine Di(2-ethylhexyl)ethanolamine Monoisopropanolarnine Diisopropanolamine Triisopropanolamine Dimethyl isopropanolamine Dibutyl isopropanolamine Hexylarnine Dihexylamine Monoethanolamine Diethanolarnine Triethanolamine N.-methyl ethanolamine Dimethyl ethanolarnine N-et y e hanqlam n N-e h Ld st hanQhm N methyl diethan'olamine n-Amylamine Dodecylamine 2-amino-4-methylpentane 4-aminq-2-but anol 3 5-isopropylamino-1-pentanol i r i i N-butylaniline Similarly, secondary high molecular weight aliphatic amines known as Armeen 2C and Armeen 2HY, as described in circular entitled secondarysArmeens, as issued by Armour Chemical Division, Chicago, Illinois.

Also, high molecular weight aliphatic amines known as Armeen 10, Armeen 16D, Armeen HTD, Armeen 18D, and Armeen CD, as described in a pamphlet entitled Armeens, issued by Armour Chemical Division, Ar-' mour and Company, Chicago, Illinois. 1

Suitableramin'es having anaromatic ring includealphamethylbenzylamine, alpha 5 methylbenzylmonoethanolamine and alpha-methylbenzyl diethanolamine.

One may use tertiary alkylprimary amines such as. tertiary-octylamine', alkylamine 81-R, alkylamine .81T, alkylamine JM-R, and alkylamine JM-T. As to a description of these amines see Rohm & Haas Company, Philadelphia, Pa., pamphlet entitled Tertiary-'Alkyl Primary Amines. Z

Other amines include: 2-amino-2-methy1-l-propanol 2-amino-2-methyl-1,3-propanediol. Z-amino-Z-ethyl-1,3-propanediol 3-amino-2-methyl-l-propanol r 2,489,672, dated November 29, 1949, to Revukas.

Further examples of this same type of material, which: has available both a phenolic hydroxyl and an alkanol hy-' droxyl, :are the condensation products derived from a phenol, either monofunctional or difunctional,"such'as para-tertiary butylplienol, para-tertiary amylphenol, octylphenol nonylphenol, and similar phenols having a sub-' stituent such as two butyl groups or'two nonyl groups in both an ortho and the para position. Such phenols are reacted with an aldehyde, such as formaldehyde, acetal-L dehyde, etc.,-and an alkanol amine, such as diethanol j amine, ethylethanolamine, dipropanolamine, and other amyl amines having only one amino hydrogen atom. See,

for example, U. S. Patent No. 2,457,634, dated December 28, 1948, to Bond et al.

Amines having ring structures of course include aniline, diphenylamine, cyclohexylamine, dicyclohexylamine, and various comparable amines with alkyl substituents in the 1mg.

Other suitable amines are those obtain'ed'fro'm sugars or comparable derivatives, such as glucamine and maltosar'nine. A product such as glucose can be reacted with a primary amine such as hexylamine, octylamine, decylamine, dodecylamine, or the like, and then subjected to reduction so'as to give other suitable primary amines which in turn can be subjected to oxyalkylation. Methyl-- glucamine can be. reacted with an alkylene oxide so as toreplace thegamino hydrogen atom by the hydroxyethyl, hydroxypropyL'or similar radical, to yield a very valuable type of monoamine.

.Asmonoainine ;compound may be combined with an alkylene oxide so the resultant product may have a molecular weight as high as 3600 or thereabouts, or even higher. Note, for example, the oxyalkylated amine described in U. S.--Patent 2,679,510, dated May 25, 1954,. to De Gro'ote. The selected compounds may be cyclic:

gr ngy-cyclic, Thgse which are cyclic may be heterocyclicf as in the case ofmorpholine derivatives or oxazolines ethanol's. This would applyrwhere instead of being a derivativedfiiionoethanolaminethe oxazoline was a derivative ofa' low molal acid or a high molal acid and 2-amino-2-methyl-1,3-propanediol.

which'may be regarded as derivatives of N-acyI-Z-amirio- Another particularly valuable reactant is obtained by reactingtris(hydroxymethyl)aminoethane with 5, 10, or

15 moles of ethylene oxide.

Note, again, where primary or secondary amines are herein included, the actual reactants are such amines in combination with at least sufficient alkylene oxides, prefer- .ably having not over 8 carbon atoms to convert them into tertiary amines, having of course at, least one reactive hydrogen atom.

The olefin oxides most readily available are, of course, ethylene, propylene, and butylene. However, one may also use styrene oxide and recently there has become available olefine oxides having 5 carbon atoms, i. e., pentene oxide and also a product which is commonly referred to as diisobutylene oxide. It is, in fact, a mix ture of 1,2-epoxy-2,4,4-trimethylpentane and 2,3-epoxy .2,4,4-trimethylpentane.- Glycide can be employed and; of course, is a means of producing tertiary alkyl amines having more than 3 hydroxyl radicals.

One also canv produce suitable tertiary amines in which'more than one olefin is employed, for instance, propylene 'oxide and ethylene oxide, or butylene oxide and ethylene oxide,'jor

' any. other combination with or without the use of glycide.

Attention is again directed to the fact that monoamines'of the kind herein described can be reacted with 1, 2, or 3 oxirane rings and the product so. obtained may greatly increase the hydrophobe character of 'theacyl radical to which it; is attached or it may oflset the hydro-. phobe character by introducing a highly hydrophile group. V a a a 7 Examples of tertiary amines in which the nitrogen atom is not basic or at least not basic incomparison with triethanolamine, or compounds such as phenyl diethanolamine, phenyl dipropanolamine, phenyl dibutanolamine, or derivatives thereof, obtained by reaction with the olefine oxides previously mentioned. H 2

BARB;

'or" 'epoxidized products" These products are epoxybutyl stearate, isobutylepoxyace'toxy stearate-and methylepoxy soyate. These products can be reacted with tertiary monoamines having a reactive hydrogen atom such as- ...triethanolamine, and other comparable monoamines- Our preference is to react such epoxidized compound with b si hydrqxylated monoamino compounds as previously noted. ..There fore,i*the.bulk of this part-will 'be:c0n- :cerned with examples illustrating this type.

As previously: pointed out the reaction involving 'the reactant containingathe oxirane ring and the selected 12 quired act as their own catalyst. As h'a's -b'een pointed out elsewhere catalysts can be added, particularly alkaline catalysts such as sodium methylate, eaustic-soda,fcaustic potash, etc. In a general Way, the procedure employed compound having a labile hydrogen atom is essentially '5 in preparing the reactants is the same and the only prea variety of oxyalkylation. For this reason the. reactions caution taken as a rule is to avoid temperatures above are so conducted. The procedure is simpler than is the that required to rupture the 'oxirane ring for the reason case when ethylene oxide or propylene oxide is used for that side reactions or secondary reactions may take place. the reason that the reactants are non-volatile as a rule The procedure is illustrated by examples 1a and 15a, and thus one does not have to use an autoclave or simi- 10 and then by Tables I, II and III which present the data lar equipment. Furthermore, many of the reactants emcovering the preparation of a Wide variety of products ployedare basic in character and thus to the extent refrom the reactants described previously.

TABLE I Catalyst Ex. Oxirane ring Amt, Hydroxylated Tertiary Amt, sodium Temp., Time, Product of reaction No. containing ester gms. monoamine gms. methox- 0. hrs.

ide, gms.

1a Epioxybtutyl 258 Ethyldiethanolamine 93 1:8 165 3. 5 Amber vise. liq. xyl. and ale. sol. s eara e.

246 Dlbutyl isoprpano1amlne 124 1. 8 180 3 Brn. vise. liq. xyl. and ale. sol. 258 Triethanolamine 105 1. 8 155 -3 Dk. brn. vise. liq. xyl. and ale. Sol. 258 do 52 1. 5 160 '3 Lt. brn. vise. liq. xyl. and ale. sol. 184 Oetylarnine-i-4-ethylen e 152 1. 7 165 4 Dk. red vise. liq. xyl. and aloe. sol. 147 Tris(hydroxymethyl)amino 232 1. 9- 160 4 Dk. yel. vise. liq. xyl. and'ale. sol.

methane+10 ethylene oxide. 246 Morpholine+5 ethylene oxide. 204 2. 2 170 3 Brn. vise. liq. xyl. andale. sol. 246 Octylamine+2 glycide 186 2. 1 160- 4 Dk. yel. vise. liq. xyl. and ale. sol. 184 Triethanolamine-l-Z glyeide- 148. 5 1.7 160 4 Dkftlbrn. glassy plaste, sol. in isopropanol,

s y. so 1J1 xy 184 Dibutylamine+1 glyeide 101. 5 1. 4 155 3 Dk.-red vise. liq. -xyl. and ale. sol. 147 Ethomeen S/ 196 1. 7 160 4 Yel. vise. liq. xyl. and ale. sol. 184 Abietlyl amine+2 ethylene 202 1.9 165 4 Yel. soft solid, xyl. and ale. sol.

OX1 8. 184 Diphgnylamine+4 ethylene 172 1.8 v 165 3 Lt. brn.-visc. liq. xyl. and-alc. sol.

oxr e. 184 Armeen 18D+2 glycide 199 1. 9 160 4 Yel. vise. liq. xyl. and alc. sol.

TABLE II Catalyst Ex. Oxirane ring Amt, Hydroxylated Tertiary Amt., sodium Temp, Time, Product of reaction No. containing ester gms. monoamlne gms. methox- 0. hrs.

. ide, gms.

15m... Isobutylepoxy 287 Tri-isopropanolamine 95. 5 1. 9 160 3 Lt. brn. vise. liq.

aeetoxy stearate. 16a. 287 N,N-dibutyl ethanolamine.. 86. 7 1. 9 175 3 Amber color vise. liq. xylene and alc. sol.

287 N ,N di(hydroxyethyl) hexyl- 85. 5 1. 9 165 3. 5 Dk. brn. vise. liq. xyl. and ale. sol.

amine. 198 N,N-di(hydroxy isopropyl) 101 1. 5 170 3 Dk. red vise. liq. xyl. and ale. sol.

lauryl amine. 287 NLN diliydroxyethylamino 89 1. 9 160 3 Dk. yel. vise. liq. xyl. and alc. sol.

utano 287 N -phenyldiethanolamine 90 1. 9 165 3 Dk. red vise. liq. xyl. and alc. sol. 287 N -cyelohexyldiethanolamine. 101. 5 2.0 165 3 Amber color vise. liq. xyl. and ale. sol. 287 N-butyl diethanolamine 80. 5 1. 9 3. 5 o. 198 Laurylamine+2 g1yeide 111 1. 6 160 3 Dk. brn. vise. liq. ale. and xyl. sol. 198 Abietylamine+2 glycide. 155 1. 8 4 Lt. yel. vise. liq. xyl. and ale. sol. 118. 6 Ethomeen 0/25 182. 6 1. 5 165 4 Do.

19 Cyclo1hexylamine+2 ethylene .82 1. 4 160 3. 5 Brown vise. liq. xyl. and ale. sol.

OX1 e. 198 Morpholine+5 ethylene oziide 102 1. 5 3 Dk. amber vise. liq. xyl. and ale. sol. 198 Diisopropanolamine+10 eth- 191 2 165 4 Dk. yel. vise. liq. alc. sol. Slty. benzene ylene oxide. sol.

TABLE :III

Ex. Com- Amt., Amt., Mplal Temp., Time, N 0. pourrlld gms. Amino compound gms. ratio 0. -hrs. Product of reaction use 1b. 1a".-. 167 Hydroxyethyl ethylene di- 347 1:1 200 2 Elk. soft solid, sol. in ale. sltly. sol. amine. 200-240 1 inwtr.

240-310 1 2b 3a 173 Diethylene triamine 34.15 1:1 200 2 Dk.brn. softsolid. S01.l.ua1e.sltly.

' 200-240 1 sol. in wtr.

. 240-315 1 3b. 4a 221.5 -do 51.6 112' 0 2 Greenish-blk. pasty solid. Sltly. sol.

200-240 '1 in water. 240-310 1 4b. 5a 225.5 Octylamine 43 1:1 0 1 Dkramber vise. liq. sol. in xyl. and 200-230 2. 5 ale. 5b.... 7a 337. 5 Sodium hydroxide water 358 5 1: 1 95-98 3 50% soln.-elear yel. gel. 6b-... 8a..... 323.5 Egg i i Dk. brnzvisc. liq. xyl. and ale. sol. 7b 9a 221.5 Trlethanolemine 49.7 1:1 g 1311;. soft solid, xyl. and ale. sol. .-8b. 1041-... 190 Hydroxyethyl ethanola- 34. 7 1:1 ;200 2 Dk. bru. soft solid, alc. sol. and sltly.

mine. 200-240 1 xyl. sol.

' 240-305 1 I 9b. 5b 139 10% B501: 210 111 90-95 2 Yellowish gray solid, sol. inhot alc.

i h "and ale. xyl. mix. In'sol. in wtr. 105.... 13a.-. .181 .-Tetraet hylene' pentamme..- 47.2 =1:1 200 223 'Blk.-'-soft solid, xylnand-alezzsol.

active.

Example 1a A 500 ml. 3-neckedflask was fitted with a reflux condenser, a thermometer and an eflicient sealed stirrer. In the flask was place'd 258 gramsof epoxybutyl stearate, 93 grams of ethyl diethanolamine and 1.8 grams of sodium methoxidej The epoxy butyl stearate contained Example 15a:

In the same equipment, setup as used in Example 1a, 287 grams of isobutylepoxyacetoxy stearate and 95.5 grams of triisopropanolamine were reacted at 160" C. in the presence of 1.9 grams of sodium methoxide. The epoxy ester contained 2.7% oxii-ane oxygen or one oxirane ring per 593 grams. At the end of 3 hours heating the reaction was completed. The product was a light brown viscous liquid, soluble in xylene and alcohol. It was surface active and more oil soluble than the product from Example In.

Example 1b In a 300 ml. 3-necked flask, equipped with a Barrett type distillation receiver, a condenser, a thermometer and a sealed stirrer, 34.7 grams of hydroxyethyl ethylene diamine was reacted with 167 grams of the reaction product obtained from Example 1a.- The reaction temperature was first maintained at 200 C. for 2 hours, then raised to 240 C. in another hour. During this heating,

butyl alcohol was distilled over. When the temperature reached 240 C. the distillation of butyl alcohol ceased but gradually water began to collect in the distillation receiver forming a bottom layer. The heating was continued while a'slow stream of nitrogen was introduced into the flask through a side tube. When the temperature reached 310 C. no more'distillate was collected. The reaction was considered complete. The distillate consisted of 25.5 grams of yellow colored alcohol layer and 5.8 grams of water layer. The product was a black color glassy solid. It was soluble in alcohol and xylene alcohol mixture, and slightly soluble in xylene or water.

Example 5b 246 grams of epoxybutyl stearate and 204 grams of action product, 259.5 grams of 7.7% sodium hydroxide was added. This heterogeneous mixture wasfirst reacted at 9598 C. under slight reflux until a clear homogeneous solution was obtained. Then it was heated for another hour more to insure complete reaction. The total time of. heating was 3 hours. The product, 50% in concentration, was a clear yellow gel. It was soluble in alcohol and formed a semi-permanent emulsion of water in xylene.

PART 4 The herein described amines are almost invariably and inevitably basic but some exceptions are amines of a type such as phenyl diethanolamine, phenyl dipropanolamine, etc. Our preference is to use the cheaper and more readily available amines, such as ethyl diethanolamine, methyl diethanolamine, triethanolamine, tripropano-lamine, etc. The final products show little basicity and, generally speaking, the addition of a mole of acid such as acetic acid or the like per nitrogen atom, even when a basic amine, is employed, such as triethanolamine, is

.apt to yield .a salt plus some free acid. Thus, it is possible to add a high molal acid or low molal acidsoas to form a salt with the residual basicity. In anumber of instances salt formation changes or alters the solubility of the free base in either oil or ,water and for a number of purposes makes the salt form more attractive. Where the base has a plurality of basic nitrogen atoms one can neutralize one or mdreas desired. Thus, the basic prodnets of reaction ,can be reacted with low molal acids such as acetic acid, lactic acid, glycolic acid, prop'ionicacid, diglycolic acid, and the, like. On the other hand, one can use naphthenic acid," higher fatty acids, .tall oil sulfonic acids, and particularly oil soluble petroleum sulfonic acids such as mahogany acids, toform salts.

. Table IV following shows combinations of products which appeared in prior tables combined with various acids illustrating what has been said, in this part ofthe text.

TABLE IV Comi i Isoprotion pound Amt, Acid used Amt, panol concen- No. gms. i gms. used, tration,

, gms. percent 1a 50 Acetic acid 6.27 56.27 50 211 50 do 5.67 55.67 50 3a -50 Glycollc acid 70% 12.1 54. 90 50 a 50 do 6.63 52.0 50 8a 50 Lactic acid 7.37 57.37 50 10a- 50 d0 8.30 58.30 [50 16a- 50 D1glycolieacid 4. 54. 80 50 17m--- 50 do 4.82 54.82 50 21a 50 Dinonyl naphthalene sul- 31.7 81.70 50 ionic acid. 2211.--- 50 do 33.4 83.40 50 PARTS The products herein described fall into two classes; those which are basic by virtue of the presence of one or more basic nitrogen atoms and those which either are not basicor the amino radical does not have significant basicity. Thus, what'is said herein applies not only to compounds as such but also tothose which are basic enough to form salts and also applies to the salts as described in Part 4, preceding. Such products and others herein described may all be used for the resolution of petroleum emulsions of the water-in-oil type. The products without further reaction are particularly valuable as additives for lubricating oils which are derived from sources other than petroleum.

As to specific uses for the herein described compounds including the various salts it is to be noted such com pounds are valuable as a fuel oil additive in the manner described in U. S. Patent 2,553,183, dated May 15, 1951, to Caron et al. It can be used in substantially the same proportions or lower proportions and this is particularly true when used in conjunction with glyoxalidine or amido glyoxalidine.

An analogous use in which these products are equally satisfactory is than described in U. S. Patent No.

2,665,978, dated January 12, 1954, to Stayner et al. The

amount employed is in the same proportion or lesser amounts than referred to in said aforementioned Caron et al. patent.

The second use is for the purpose of inhibiting fogs in hydrocarbon products as described in U. S. Patents Nos. 2,550,981 and 2,550,982, both dated May 1, 1951, and. both to Eberz. same proportions as herein indicated or even small proportions.

A third use is to replace oil soluble petroleum sulfonates, so-called mahogany soaps, in the preparation of certain emulsions, or soluble oils or 'emulsifiable lubricants where Such h n 1 5 e s e/e T e os ns k m re,

Here again it can be used in the i 15 I, tu'r'es having this peculiarjproperty serve to replace all or a'substantial part of the mahogany soap.

Another use is where the product 'does not'serve as an emulsifying agent alone but serves as an adjunct.

Briefly stated, the fourth use is concerned with use as a coupling agent to be employed with an emulsifying agent. See The Composition and'Structure of TechnicalEmulsions, J. H. Goodey, Roy. Australian Chem. Inst., J. and Proc., vol. 16, 1949, pp. 47-75. As 'statedin the summary of this article, it reads:

The technical'oil-in-water emulsion is regarded as a system of four components: the dispersion medium, consisting of the highly polar substance water; the disperse phase composed of hydrocarbons or other substances of comparativelyweak polarity; the coupling agent, being an oil-soluble substance involving an hydroxyl, carboxyl or similar polar group; and the emulsifyinga'g'ent, which is a water-soluble substance involving an hydrocarbon radical attached to an ionizable group.

Such compounds or derivatives also are effective for other purposes such as an anti-fogging agent in motor fuels,a coagulation preventive inburner oils, and as an additive for the prevention of corrosion of ferrous metals. Such invention, however, is not part of what is herein claimed.

The herein described products and the derivatives thereof are particularly valuable in flooding processes forrecovery of oil from subterranean oil-bearingstrata when employed in the manner described in U. "S; PatentjNo. 2,233,381, dated February 25, 195 1, to De Groote and Keiser. I v i '1 Furthermore, the herein described products may be-employed to increase operating efliciency "by increasing the oil-to-brine ratio or by increasing the total oil recovery in primary recovery operations as differentiated from secondary recovery operations. The procedures employed are essentially those as described in either U. S. Patent No. 2,331,594, dated October 12, 1943, to Blair,-or U. S. Patent No. 2,465,237, dated March'22, 1949, to Larsen.

When the products of the kind herein described are used for water flooding and 'particularly'in the form of salts, they have unusual value in a fresh water or brine system for the inhibition of the growth of bothjanaerobic and aerobic bacteria-but are particularly applicable in controlling the sulfate reducing organisms which cause difiiculty in secondaryj recovery operations. Thus, one may use some other agent or agents in water floodsysterns and use compoundsas hereindescribed primarilyifor reducing bacterial growth. {The use of'such industrial bactericide is well known and the procedure is conventional;- for instance,one can use the methods described in an article entitled The Role of Microorganismsflby R. C. Allred, which appeared in Producers Monthly, vol. 18, No. 4, pages 18-22. I

In the useof the hereindescribed products as industri'al bactericides and particularly in connection with water flood operations we prefer to use the salts obtainedwby partial or total neutralization with carboxyacids, particularly monocarboxy acids having not over f6"carbon atoms and preferably a hydroxylated acid such as hydroxyacetic acid.

Specific attention is directed to the article entitled Preparation of Water for Injection. Into Water Reservoirs, which appeared in the Journal of Petroleum Technology, volume 7, No. 4, page'9 (April-1955). The

author is Torrey.

PART 6 The products obtained in thejmanner herein described are valuable for various purposes as indicated in Part 5,

preceding. Where salts can be formed, i. e., where the products are basic'inch'ara' 'cter this applies to thesalts as wen as to the'unneu'tralized material. fiow'ever; one of the most important-uses for'the herein describedproducts-is as an iiltermediate for "further reaction. It is obvious that reactions of the kind described previously invariably and'inevitably yield oxyalkyl'ation susceptible compounds, products or co-generic mixtures. The reason is that when the oxiranevring is open there is produced a hydroxylgroup. This hydroxyl group is susceptible to oxyalkylation and there may be present other'groups which likewise are susceptible to oxyalkylation as,for example, when an epoxidized butyl soyate is reacted with a mole of triethanolamine and then with a mole of a polyamine such as'triethylene tetramine. Thus, the products previously described may be combined with a variety of reactants as chemical intermediates, for instance, with various diepoxides or polyepoxides. They may be combined with a number of other monoepoxides such as epichlorohydrin, styrene oxide, glycide and methylgylcide. They may be reacted with alkyl glycidyl ether, glycidyl isopropyl ether, and glycidyl phenyl ether.

Furthermore, such productsmay be reacted with alkylene imines such as ethylene imine or propylene imine, to produce cation-activematerials. Instead of an imine, one mayrtemploy 'what sis a somewhat equivalent materialyto wit, a dialkylaminoepoxypropane of the structure 7 wherein R and R arealkyl groups.

Likewise, since the products have a hydroxyl group they may be combined. by esterification with carboxy acids such as higher fatty acids, so as to change their characteristics or with polycarboxy acids, such as diglycolic, ma'leic acid, phthalic'acid,'succinic acid, and'the. like, to give resins, so ftpolymers or fractional esters which are essentiallymonomeric.

A variety of compounds can be formed by merely heating the reaction mass provided'there are free hydroxyls present-to a point where etherization takes place. This would apply, forexample, to the product obtained by reacting one mole of butyl soyate with a mole of triethanolamine. Furthermore, the fatty acid radical may act as an acylating agent and form an ester comparable to the oleic acid ester of triethanolamine. Such reaction can become complex depending on whether it is an intraor inter-molecular reaction.

As has been pointed out previously, the reaction product, for example, of one mole of triethanolamine and one mole of epoxidized butyl soyate, can be reacted with a polyamine such as triethylene tetramine, so as to form an amide which in turn may be heated so as to form an imidazoline.

Any one of the products above described can be subjected to oxyalkylation with the various epoxides previously noted. The derivatives thus obtained in the manner previously described may be used for various processes where surface-active materials in either an aqueous phase or a hydropho'be phase are indicated for the various industrial uses noted for the products per se in Part 5, preceding.

As is obvious, if products of the kind herein described, i. e., derivatives obtained, for example, fromepoxidized butyl soyate and triethanolamine or tripropanolamine, are saponified and acidified under appropriate conditions it is possible toobtain an inner salt "involving a basic amino radical and the residual carboxyl radical. However, if such product, or a suitable intermediate, or the initial product itself, is saponified with a strong base, such as caustic'so'da, or caustic potash, or the like, the resultant product ischaracterizedby the presence of the metallic ion, 'for instance, sodium or potassium, in the carboxyl position, and the amino groupis merely part. of; the acyl radical. conventional means from the herein described resultants, i. e., either the socalled free acid which in essence is really an inner salt, or the salt involving the use of sodium hydroxide, potassium hydroxide, or the like. The products so obtained, Whether metallic salts or inner salts, are effective for prevention of corrosion not only in an aerobic system but also in aerobic systems.

Also, it is to be noted that one need not use sodium hydroxide or potassium hydroxide in the above described compounds but one may also use a quaternary ammonium base, particularly a base whose basicity is greater than the terminal amino group in the acyl radical.

Also, it is to be noted that if one prepares the salts of metal, such as magnesium, aluminum, barium, or the like, the products so obtained are effective for the same purpose and particularly in a hydrophobe system, and also are valuable as additives to lubricating oils, fuel oils, and the like.

What has been said previously in regard to the formation of alkali metal salts (sodium, potassium, and lithium) V and in regard to the formation of inner salts is an oversimplification insofar that we are aware that in some instances steric hindrance prevents the formation of an inner salt but does not prevent the formation of intramolecular salts. Thus, in some instances such intra-molecular salts have unusual properties including uses for the purpose above indicated for the alkali metal salts or the inner salts.

Having thus described our invention what we claim as new and desire to secure by Letters Patent, is:

1. Products obtained by reacting under oxyalkylation conditions (A) an epoxidized ester of a lower alkanol and an acid selected from the class consisting of fatty acids and acylated fatty acids in which the epoxidized ester contains on the average approximately one oxirane ring per fatty acid radical, with (B) a hydroxylated tertiary monoamine; said reaction between (A) and (B) involving rupture of the oxirane ring and being limited to the linkage -COC-, which linkage is being characterized by freedom from a carbonyl carbon atom; said product of reaction being hydroxylated and solvent soluble.

2. Products obtained by reacting under oxyalkylation conditions (A) an epoxidized ester of a lower alkanol and a higher fatty acid derived from a naturally occurring glyceride in which the epoxidized ester contains on the average approximately one oxirane ring per fatty acid radical and in which the acyl radical of the ester is free from any residual hydroxy radical, with (B) a hydroxylated tertiary monoamine; said reaction between (A), and (B) involving rupture of the oxirane ring and being limited to thelinkage CO-C, which linkage is being characterized by freedom from a carbonyl carbon atom; said product of reaction being hydroxylated and solvent soluble.

3. Products obtained by reacting under oxyalkylation conditions (A) an epoxidized ester of a lower alkanol and a higher fatty acid derived from a naturally occurring glyceride in which the epoxidized ester contains on the average approximately one oxirane ring per fatty acid radical and in which the acyl radical of the ester is free from any residual hydroxy radical, with (B) a basic hydroxylated tertiary monoamine; said reaction between (A) and (B) involving rupture of the oxirane ring and being limited to the linkage C--OC- which linkage is being characterized by freedom from a carbonyl carbon atom; said product of reaction being hydroxylated and solvent soluble.

4. Products obtained by reacting under oxyalkylation conditions (A) an epoxidized ester of a lower alkanol and a higher fatty acid derived from a naturally occurring glyceride in which the epoxidized ester contains on the average approximately one oxirane ring per fatty Both types of products can be obtained by acid, radical and in which the acyl radical, of the ester involving rupture of the oxirane ring and being limited to the linkage -COC-, which linkage is being characterized by freedom from a carbonyl carbon atom; said product of reaction. being hydroxylated and solvent soluble.

5. Products obtained by reacting under oxyalkylation conditions (A) an epoxidized ester of a lower alkanol and a higher fatty acid derived from a naturally occurring glyceride in which the epoxidized ester contains on the average approximately one oxirane ring per fatty acid radical and in which the acyl radical of the ester is free from any residual hydroxy radical, with (B) a basic hydroxylated tertiary monoamine having at least 3 hydroxyl radicals; said reaction between (A) and (B) involving rupture of the oxirane ring and being limited to the linkage COO, which linkage is being characterized by freedom from a carbonyl carbon atom; said product of reaction being hydroxylated and solvent soluble.

6. Products obtained by reacting under oxyalkylation conditions (A) an epoxidized ester of a lower alkanol and a higher fatty acid derived from a naturally occurring glyceride in which the epoxidized ester contains on the average approximately one oxirane ring per fatty acid radical and in which the acyl radical of the ester is free from any residual hydroxy radical, with (B) a tertiary alkanol amine having at least 3 hydroxyl radicals; said reaction between (A) and. (B) involving rupture of the oxirane ring and being limited to the linkage C-O--C-- which linkage is being characterized by freedom from a carbonyl carbon atom; said product of reaction being hydroxylated and solvent soluble.

7. Products obtained by reacting under oxyalkylation conditions (A) an epoxidized ester of a lower alkanol and a higher fatty acid derived from a naturally occurring glyceride in which the epoxidized ester contains on the average approximately one oxirane ring per fatty acid radical and in which the acyl radical of the ester is free from any residual hydroxy radical, with (B) a monoarnine of the structure (C,.H ,.O)..'H

in which n is a small whole number not over 8 and n is a whole number varying from one to 50 said reaction between (A) and (B) involving rupture of the oxirane ring and being limited to the linkage CO-C, which linkage is being characterized by freedom from a carbonyl carbon atom; said product of reaction being hydroxylated and solvent soluble.

8. Products obtained by reacting under oxyalkylation conditions (A) an epoxidized ester of a lower alkanol and a higher fatty acid derived from a naturally occurring glyceride in which the epoxidized ester contains on the average approximately one oxirane ring per fatty acid radical and in which the acyl radical of the ester is free from any residual hydroxy radical, with (B) a monoamine of the structure (CHHMOYH N(C,.H:1.

(cannons in which n is a small whole number not over 8; said reaction between (A) and (B) involving rupture of the oxirane ring and being limited to the linkage -C--O--C which linkage is being characterized by freedom from 19 20 acarbo1iyl carbon atom; said product of reaction being 7 References Cited in the file of this patent hydroxylated and solvent soluble.

9. The product of claim 8 with the proviso that 11 UNITED STATES PATENTS is 2. 2,445,892 Swern et a1. July 27, 1948 10. The product of claim 8 with the proviso that n 5 2,646,405 Hughes July 21, 1953 is 3. 2,712,535 Fisch July 5, 1955 

1. PRODUCTS OBTAINED BY REACTING UNDER OXYALKYLATION CONDITIONS (A) AN EPOXIDIZED ESTER OF A LOWER ALKANOL AND AN ACID SELECTED FROM THE CLASS CONSISTING OF FATTY ACIDS AND ACYLATED FATTY ACIDS IN WHICH THE EPOXIDIZED ESTER CONTAINS ON THE AVERAGE APPROXIMATELY ONE OXIRANE RING PER FATTY ACID RADICAL, WITH (B) A HYDROXYLATED TERTIARY MONOAMINE; SAID REACTION BETWEEN (A) AND (B) INVOLVING RUPTURE OF THE OXIRANE RING AND BEING LIMITED TO THE LINKAGE -C-O-C-, WHICH LINKAGE IS BEING CHARACTERIZED BY FREEDOM FROM A CARBONYL CARBON ATOM; SAID PRODUCT OF REACTION BEING HYDROXYLATED AND SOLVENT SOLUBLE. 